{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,29]],"date-time":"2026-04-29T20:47:46Z","timestamp":1777495666365,"version":"3.51.4"},"reference-count":77,"publisher":"Wiley","issue":"32","license":[{"start":{"date-parts":[[2021,5,17]],"date-time":"2021-05-17T00:00:00Z","timestamp":1621209600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2021,6,4]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Fluorinated heterocycles have attracted much attention in the pharmaceutical and agrochemical industries. Many strategies have already been developed to achieve the synthesis of fluorinated heterocycles. Formidable challenges remain, however, in the synthesis of fluorinated isocoumarin derivatives that are among the most alluring structural motifs. Herein, the indium\u2010catalyzed C\u2212F bond transformation of 2\u2010(2,2\u2010difluorovinyl) benzoates is reported, which are readily accessible compounds, to give a diverse array of fluorinated isocoumarins. The present reaction proceeds smoothly using inexpensive reagents: a catalytic amount of indium salt in the presence of zinc salt. A theoretical calculation of potential energy profiles showed that the reaction consists of oxymetalation with the elimination of alkyl halide and the \u03b2\u2010fluorine elimination.<\/jats:p>","DOI":"10.1002\/chem.202100672","type":"journal-article","created":{"date-parts":[[2021,4,15]],"date-time":"2021-04-15T06:53:12Z","timestamp":1618469592000},"page":"8288-8294","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":11,"title":["Indium\u2010Catalyzed C\u2212F Bond Transformation through Oxymetalation\/\u03b2\u2010Fluorine Elimination to Access Fluorinated Isocoumarins"],"prefix":"10.1002","volume":"27","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-2470-4905","authenticated-orcid":false,"given":"Tetsuji","family":"Yata","sequence":"first","affiliation":[{"name":"Department of Applied Chemistry, Graduate School of Engineering Osaka University  2-1 Yamadaoka, Suita Osaka 565-0871 Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7182-0503","authenticated-orcid":false,"given":"Yoshihiro","family":"Nishimoto","sequence":"additional","affiliation":[{"name":"Department of Applied Chemistry, Graduate School of Engineering Osaka University  2-1 Yamadaoka, Suita Osaka 565-0871 Japan"},{"name":"Innovative Catalysis Science Division Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI) Osaka University Suita  Osaka 565-0871 Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Kouji","family":"Chiba","sequence":"additional","affiliation":[{"name":"Material Science Division, MOLSIS Inc.  1-28-38 Shinkawa, Chuo-ku Tokyo 104-0033 Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6618-2893","authenticated-orcid":false,"given":"Makoto","family":"Yasuda","sequence":"additional","affiliation":[{"name":"Department of Applied Chemistry, Graduate School of Engineering Osaka University  2-1 Yamadaoka, Suita Osaka 565-0871 Japan"},{"name":"Innovative Catalysis Science Division Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI) Osaka University Suita  Osaka 565-0871 Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2021,5,17]]},"reference":[{"key":"e_1_2_9_1_1","doi-asserted-by":"crossref","unstructured":"P. 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Ojima Fluorine in Medicinal Chemistry and Chemical Biology Wiley-Blackwell Chichester 2009;","DOI":"10.1002\/9781444312096"},{"key":"e_1_2_9_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/jm800219f"},{"key":"e_1_2_9_5_2","doi-asserted-by":"publisher","DOI":"10.1039\/B610213C"},{"key":"e_1_2_9_6_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.1131943"},{"key":"e_1_2_9_7_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201206566"},{"key":"e_1_2_9_7_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201206566"},{"key":"e_1_2_9_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr500209t"},{"key":"e_1_2_9_9_1","unstructured":"For examples of synthesis of fluorinated heterocycles see:"},{"key":"e_1_2_9_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.8b01121"},{"key":"e_1_2_9_11_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.7b00335"},{"key":"e_1_2_9_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b00118"},{"key":"e_1_2_9_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol5035518"},{"key":"e_1_2_9_14_1","unstructured":"For selected reviews see:"},{"key":"e_1_2_9_15_2","doi-asserted-by":"publisher","DOI":"10.2174\/138527211794518970"},{"key":"e_1_2_9_16_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.201800019"},{"key":"e_1_2_9_17_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-0039-1690816"},{"key":"e_1_2_9_18_1","unstructured":"\u00a0"},{"key":"e_1_2_9_19_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jfluchem.2014.03.008"},{"key":"e_1_2_9_20_2","doi-asserted-by":"publisher","DOI":"10.1134\/S107042800811016X"},{"key":"e_1_2_9_21_2","doi-asserted-by":"publisher","DOI":"10.1134\/S1070428019080086"},{"key":"e_1_2_9_22_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202013052"},{"key":"e_1_2_9_22_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.202013052"},{"key":"e_1_2_9_23_1","unstructured":"\u00a0"},{"key":"e_1_2_9_24_2","first-page":"749","volume":"120","author":"Cerichelli G.","year":"1990","journal-title":"Gazz. Chim. Ital."},{"key":"e_1_2_9_25_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jfluchem.2003.07.001"},{"key":"e_1_2_9_26_1","unstructured":"\u00a0"},{"key":"e_1_2_9_27_2","unstructured":"T. Rueckle X. Jiang P. Gaillard D. Church T. Vallotton US Pat. Appl. US20060122176\u2005A1 2006;"},{"key":"e_1_2_9_28_2","unstructured":"A.\u2005D. Borthwick R.\u2005J. Hately D.\u2005M.\u2005B. Hickey J. Liddle D.\u2005G.\u2005H. Livermore A.\u2005M. Mason N.\u2005D. Miller F. Nerozzi S.\u2005L. Sollis A.\u2005K. Szardengings P.\u2005G. Wyatt US Pat. Appl. US20050148572\u2005A1 2005."},{"key":"e_1_2_9_29_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.bmc.2012.09.026"},{"key":"e_1_2_9_30_1","unstructured":"\u00a0"},{"key":"e_1_2_9_31_2","first-page":"21","author":"Badland M.","year":"2011","journal-title":"Bioorg. Med. Chem. 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Moore C.\u2005C. Lu J. Am. Chem. Soc.2020 142 11641\u201311646.","DOI":"10.1021\/jacs.0c04937"},{"key":"e_1_2_9_51_1","unstructured":"A certain amount of precipitate was observed in reaction mixture after completing reaction. As the indium salt is fluorinated via \u03b2-fluorine elimination the indium salt become less soluble in toluene weakening the catalytic activity. In addition DFT calculation were performed to estimate the interaction between gem-difluorostyrene and InF3 but the InF3complex was not found whereas InI3-complex was obtained. Thus we conclude that InF3does not have a \u03c0-Lewis acidity enough to proceed the cyclization reaction and not suitable as a catalyst for our reaction system."},{"key":"e_1_2_9_52_1","unstructured":"\u00a0"},{"key":"e_1_2_9_53_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol8019567"},{"key":"e_1_2_9_54_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201704789"},{"key":"e_1_2_9_54_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201704789"},{"key":"e_1_2_9_55_1","unstructured":"\u00a0"},{"key":"e_1_2_9_56_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.9b00566"},{"key":"e_1_2_9_57_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo01298a041"},{"key":"e_1_2_9_58_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-2002-33912"},{"key":"e_1_2_9_59_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-0032-1316910"},{"key":"e_1_2_9_60_2","doi-asserted-by":"publisher","DOI":"10.1039\/C39920000348"},{"key":"e_1_2_9_61_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-2006-926458"},{"key":"e_1_2_9_62_2","doi-asserted-by":"publisher","DOI":"10.1039\/a703110f"},{"key":"e_1_2_9_63_2","doi-asserted-by":"publisher","DOI":"10.1246\/cl.2002.282"},{"key":"e_1_2_9_64_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-1139(03)00138-6"},{"key":"e_1_2_9_65_2","doi-asserted-by":"publisher","DOI":"10.1039\/C5CC02073E"},{"key":"e_1_2_9_66_2","doi-asserted-by":"publisher","DOI":"10.1039\/C39920000348"},{"key":"e_1_2_9_67_1","unstructured":"InI3could be generated in the presence of InCl3and ZnI2and can act as a gem-difluoroalkene activator (see Supporting Information)."},{"key":"e_1_2_9_68_1","unstructured":"The reaction mixture was monitored by1H NMR after completing the reaction in a sealed NMR tube to observe the quantitative generation of MeI without MeF."},{"key":"e_1_2_9_69_1","unstructured":"\u00a0"},{"key":"e_1_2_9_70_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol060912r"},{"key":"e_1_2_9_71_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201102210"},{"key":"e_1_2_9_71_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201102210"},{"key":"e_1_2_9_72_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.5b02426"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.202100672","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/chem.202100672","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.202100672","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T21:23:30Z","timestamp":1760304210000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.202100672"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2021,5,17]]},"references-count":77,"journal-issue":{"issue":"32","published-print":{"date-parts":[[2021,6,4]]}},"alternative-id":["10.1002\/chem.202100672"],"URL":"https:\/\/doi.org\/10.1002\/chem.202100672","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2021,5,17]]},"assertion":[{"value":"2021-05-04","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2021-05-17","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}]}}